Pigment dispersants based on diketopyrrolopyrrole compounds and pigment preparations

ABSTRACT

The invention provides novel pigment dispersants of the formula (I): 
                 
 
in which Q is a radical of the formula (Ia): 
                 
     s is a number from 0.1 to 4.0 and   n is a number from 0 to 2.0;
 
and provides pigment preparations comprising an organic base pigment and a pigment dispersant of the formula (I).

CROSS REFERENCE TO RELATED APPLICATION

This application is divisional application of co-pending U.S.application Ser. No. 10/375,573, filed Feb. 27, 2003, which is acontinuation application of co-pending U.S. application Ser. No.09/727,960, filed Dec. 1, 2000, abandoned.

BACKGROUND OF THE INVENTION Field of the Invention

The present invention relates to novel pigment dispersants and pigmentpreparations having improved coloristic and rheological properties andto their preparation and use for pigmenting high molecular massmaterials.

Pigment preparations are combinations of pigments and pigmentdispersants that are structurally analogous to pigments and aresubstituted by groups having a specific activity. The dispersants areadded to the pigments in order to facilitate their dispersion in theapplication media, especially in varnishes, and to improve therheological and coloristic properties of the pigments. The viscosity ofthe highly pigmented paint concentrate (millbase) is lowered and theflocculation of the pigment particles reduced. This makes it possible,for example, to enhance the transparency and gloss. Such enhancement isparticularly desirable in the case of metallic pigments.

There are a large number of proposals for improving the rheological andcoloristic properties of organic pigments by adding pigment dispersants,but they do not always lead to the result hoped for.

For instance, EP-A-0 321 919 describes the production of pigmentpreparations by mixing the base pigments with pigment derivativescontaining methyleneimidazolyl groups. EP-A-0 877 058 describes thepreparation of carboxamido-containing pigment dispersants, and pigmentpreparations comprising these pigment dispersants.

DE-A-3 106 906 describes the preparation of sulfonamido-containingpigment dispersants. Pigment dispersants based on diketopyrrolopyrrolecompounds, however, are not mentioned.

JP H3-26767 describes sulfonamido-containing pigment dispersants basedon diketopyrrolopyrrole compounds. The pigment preparations producedwith them, however, do not meet every requirement imposed on pigmentpreparations in respect of the performance properties. For instance,their solvent fastness and fastness to overcoating is inadequate, sogreatly restricting their universal application.

SUMMARY OF THE INVENTION

There was a need for improvement, and, accordingly, the object was toprovide pigment preparations which overcome the abovementioneddisadvantages of the prior art.

It has been found that the object is achieved, surprisingly, by means ofpigment dispersants based on specific diketopyrrolopyrrole compounds.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The invention provides pigment dispersants of the formula (I):

in which Q is a radical of the diketopyrrolopyrrole compound of theformula (Ia):

-   s is a number from 0.1 to 4.0,-   n is a number from 0 to 2,-   E⁺ is H⁺ or the equivalent M^(m+)/m of a metal cation M^(m+) from    main groups 1 to 5 or transition groups 1 or 2 or 4 to 8 of the    periodic system of the chemical elements, m being 1, 2 or 3, such    as, for example, Li¹⁺, Na¹⁺, K¹⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Mn²⁺,    Cu²⁺, Ni²⁺, Co²⁺, Zn²⁺, Fe²⁺, Al³⁺, Cr³⁺ or Fe³⁺; an ammonium ion    N⁺R⁹R¹⁰R¹¹R¹², where the substituents R⁹, R¹⁰, R¹¹ and R¹²    independently of one another are each a hydrogen atom, C₁-C₃₀-alkyl,    C₂-C₃₀-alkenyl, C₅-C₃₀-cycloalkyl, phenyl, (C₁-C₈)-alkyl-phenyl,    (C₁-C₄)-alkylene-phenyl, such as benzyl, or a (poly)alkyleneoxy    group of the formula —[CH(R⁸⁰)—CH(R⁸⁰)—O]_(k)—H, in which k is a    number from 1 to 30 and the two radicals R⁸⁰ independently of one    another are hydrogen, C₁-C₄-alkyl or, if k is >1, a combination    thereof, and in which alkyl, alkenyl, cycloalkyl, phenyl or    alkylphenyl R⁹, R¹⁰, R¹¹, and/or R¹² may be substituted by amino,    hydroxyl and/or carboxyl;-   or where the substituents R⁹ and R¹⁰, together with the quaternary    nitrogen atom, are able to form a five- to seven-membered saturated    ring system containing, if desired, further heteroatoms from the    group consisting of O, S and N, said system being, for example, of    the pyrrolidone, imidazolidine, hexamethyleneimine, piperidine,    piperazine or morpholine type;-   or where the substituents R⁹, R¹⁰ and R¹¹, together with the    quaternary nitrogen atom, are able to form a five- to seven-membered    aromatic ring system, containing, if desired, further heteroatoms    from the group consisting of O, S and N, and to which additional    rings may be fused if desired, said ring system being, for example,    of the pyrrole, imidazole, pyridine, picoline, pyrazine, quinoline    or isoquinoline type; or in which E⁺ defines an ammonium ion of the    formula (Ic):    in which-   R¹⁵, R¹⁶, R¹⁷ and R¹⁸ independently of one another are hydrogen or a    (poly)alkyleneoxy group of the formula —[CH(R⁸⁰)—CH(R⁸⁰)O]_(k)—H, in    which k is a number from 1 to 30 and the two radicals R⁸⁰    independently of one another are hydrogen, C₁-C₄-alkyl or, if k    is >1, a combination thereof;-   q is a number from 1 to 10, preferably 1, 2, 3, 4 or 5;-   p is a number from 1 to 5, where p is ≦q+1;-   T is a branched or unbranched C₂-C₆-alkylene radical; or in which T,    if q is >1, may also be a combination of branched or unbranched    C₂-C₆-alkylene radicals;    and in which the two radicals Z are identical or different and Z has    the definition Z¹ or Z⁴, where-   Z¹ is a radical of the formula (Ib):    —[X—Y]_(q)R³  (Ib)    in which-   X is a C₂-C₆-alkylene radical, a C₅-C₇-cycloalkylene radical, or a    combination of these radicals, it being possible for these radicals    to be substituted by from 1 to 4 C₁-C₄-alkyl radicals, hydroxyl    radicals, (C₁-C₄)-hydroxyalkyl radicals and/or by 1 or 2 further    C₅-C₇-cycloalkyl radicals, or in which X, if q is >1, may also be a    combination of said definitions;-   Y is a —O—,    or —NR²— group,-   or in which Y, if q is >1, may also be a combination of said    definitions;-   q is a number from 1 to 10, preferably 1, 2, 3, 4 or 5;-   R² and R³ independently of one another are a hydrogen atom, a    substituted or unsubstituted, or partly fluorinated or    perfluorinated, branched or unbranched (C₁-C₂₀)-alkyl group, a    substituted or unsubstituted C₅-C₇-cycloalkyl group or a substituted    or unsubstituted, or partly fluorinated or perfluorinated    (C₂-C₂₀)-alkenyl group, it being possible for the substituents to be    hydroxyl, phenyl, cyano, chloro, bromo, amino, C₂-C₄-acyl or    C₁-C₄-alkoxy and to be preferably 1 to 4 in number, or-   R² and R³, together with the nitrogen atom, form a saturated,    unsaturated or aromatic heterocyclic 5- to 7-membered ring    containing, if desired, 1 or 2 further nitrogen, oxygen or sulfur    atoms or carbonyl groups in the ring, being substituted if desired    by 1, 2 or 3 of the radicals OH, phenyl, CN, Cl, Br, C₁-C₄-alkyl,    C₁-C₄-alkoxy, C₂-C₄-acyl and carbamoyl, and carrying, if desired, 1    or 2 benzo-fused saturated, unsaturated or aromatic, carbocyclic or    heterocyclic rings;    and where-   Z⁴ is hydrogen, hydroxyl, amino, phenyl, (C₁-C₄)-alkylene-phenyl,    C₅-C₇-cycloalkyl or C₁-C₂₀-alkyl, it being possible for the phenyl    ring, the (C₁-C₄)-alkylene-phenyl group and the alkyl group to be    substituted by one or more, e.g., 1, 2, 3 or 4, substituents from    the group consisting of Cl, Br, CN, NH₂, OH, C₆H₅, mono-, di- or    tri-C₁-C₄-alkoxy-substituted C₆H₅, carbamoyl, C₂-C₄-acyl and    C₁-C₄-alkoxy, e.g., methoxy or ethoxy, and it being possible for the    phenyl ring and the (C₁-C₄)-alkylene-phenyl group to be substituted    by NR²R³, R² and R³ being as defined above, or the alkyl group is    perfluorinated or partly fluorinated.

Of interest are pigment dispersants of the formula (I) where s=0.2-3.0and n=0-0.5. Of particular interest are pigment dispersants of theformula (I) where s=0.5-2.5 and n=0-0.2.

Further of interest are pigment dispersants of the formula (I) wherein

-   R² and R³ independently of one another are a hydrogen atom, a    C₁-C₆-alkyl group or a C₁-C₆-alkyl group substituted by 1 or 2    substituents from the group consisting of hydroxyl, acetyl, methoxy,    ethoxy, chloro and bromo, or-   R² and R³, together with the adjacent nitrogen atom, form an    imidazolyl, piperidinyl, morpholinyl, pipecolinyl, pyrrolyl,    pyrrolidinyl, pyrazolyl, pyrrolidinonyl, indolyl or piperazinyl    ring.

Further of interest are pigment dispersants of the formula (I) wherein Xis a C₂-C₄-alkylene radical or cyclohexylene.

Of particular interest are pigment dispersants of the formula (I)wherein Z¹ has the definition —[(CH₂)₃—NH]₂—H, —(CH₂—CH₂—NH)₂H,—(CH₂)₃—NH—(CH₂)₂—NH—(CH₂)₃—NH₂,

—(CH₂)₃—N(CH₃)—(CH₂)₃—NH₂, —(CH₂)₃—O—(CH₂) ₂—O—(CH₂)₃—NH₂,—(CH₂)₃—O—(CH₂)₃—O—(CH₂)₃—NH₂, —(CH₂)₂—NH—(CH₂)₃—NH₂,—(CH₂)₃—NH—(CH₂)₂—NH₂, —(CH₂—CH₂—NH)₃—H, —(CH₂—CH₂—NH)₄—H,—(CH₂—CH₂—NH)₅—H, —(CH₂)₃—O—(CH₂)₂—O—(CH₂)₂—O—(CH₂)₃—NH₂,—(CH₂)₃—O—(CH₂)₄—O—(CH₂)₃—NH₂,

—(CH₂)₂—OH, —(CH₂)₃—OH, —CH₂—CH(CH₃)—OH, —CH(CH₂—CH₃)CH₂—OH,—CH(CH₂OH)₂, —(CH₂)₂—O—(CH₂)₂—OH or —(CH₂)₃—O—(CH₂)₂—O—(CH₂)₂—OH;—(CH₂)₂—NH₂, —(CH₂)₃—NH₂, —CH₂—CH(CH₃)—NH₂, —CH₂—C(CH₃)₂—CH₂—NH₂,

—(CH₂)₂—NH—CH₃,—(CH₂)₂—N(CH₃)₂, —(CH₂)₂—NH—CH₂—CH₃, —(CH₂)₂—N(CH₂—CH₃)₂,—(CH₂)₃—NH—CH₃, —(CH₂)₃—N(CH₃)₂, —(CH₂)₃—NH—CH₂—CH₃ or—(CH₂)₃—N(CH₂—CH₃)₂.

Further of interest are pigment dispersants of the formula (I) whereinZ⁴ is hydrogen, amino, phenyl, benzyl, NR²R³-substituted phenyl orbenzyl, C₁-C₆-alkyl, or a C₂-C₆-alkyl, phenyl or benzyl which issubstituted by 1 or 2 substituents from the group consisting ofhydroxyl, acetyl, methoxy and ethoxy, and with particular preference ishydrogen,

methyl, ethyl, propyl, butyl, benzyl, hydroxyethyl, hydroxypropyl ormethoxypropyl.

The pigment dispersants of the invention may be prepared bychlorosulfonating the diketopyrrolopyrrole compound of the formula (Ia):

and then reacting the sulfochloride with an amine of the formula (V):

in which Z is as defined above.

Examples of amines of the formula (V) which may be used are ammonia,methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine,sec-butylamine, isopentylamine, n-hexylamine, dimethylamine,diethylamine, dibutylamine, n-ethylbutylamine, β-hydroxyethylamine, β-or γ-hydroxypropylamine, n-methylethanolamine, diethanolamine,3-(2-hydroxyethylamino)-1-propanol, N-(2-hydroxyethyl)aniline,hydroxylamine, hydrazine, N,N-dimethyl-p-phenylenediamine,dimethylaminomethylamine, diethylaminoethylamine,2-ethylhexylaminoethylamine, stearylaminoethylamine,oleylaminoethylamine, dimethylaminoproyplamine, diethylaminopropylamine,dibutylaminopropylamine, diethylaminobutylamine, dimethylaminoamylamine,diethylaminohexylamine, 1-diethylamino-4-aminopentane,piperidinomethylamine, piperidinoethylamine, piperidinopropylamine,pipecolinoethylamine, pipecolinopropylamine, imidazolopropylamine,morpholinoethylamine, morpholinopropylamine, piperazinoethylamine,2-methoxyethylamine, 3-ethoxypropylamine, di-(2-methoxyethyl)amine,cyclohexylamine, N-ethylcyclohexylamine, dicyclohexylamine, benzylamine,2-phenylethylamine, 4-methoxyphenylethylamine,1-methyl-3-phenylpropylamine, 2-(3,4-dimethoxyphenyl)ethylamine,aniline, o-toluidine, p-toluidine, N-ethylaniline,3-(cyclohexylamino)propylamine, 2-(2-aminoethoxy)ethanol,2-(2-(3-aminopropoxy)-ethoxy)ethanol,3,3′-oxy-bis(ethyleneoxy)bis(propylamine), ethylenediamine,1,2-propanediamine, 1,3-propanediamine, 2,2-dimethyl-1,3-propanediamine,isophoronediamine, diethylenetriamine, triethylenetetramine,tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine,N,N-bis (3-aminopropyl)methylamine, tripropylenetetramine,3-(2-aminoethyl)-aminopropylamine,N,N′-bis-(3-aminopropyl)ethylenediamine,bis(3-dimethylaminopropyl)amine, 4,7-dioxadecane-1,10-diamine,4,9-dioxadodecane-1,12-diamine,5-amino-1,3,3-trimethylcyclohexanemethanamine or1,4-bis(3-aminopropoxy)butane.

The chlorosulfonation is judiciously conducted using chlorosulfonic acidin a weight excess of from 4 to 25 times, based on thediketopyrrolopyrrole, and preferably further adding from 1 to 10 timesthe molar amount, based on the diketopyrroloyrrole, of thionyl chloride.The chlorosulfonation is preferably conducted at a temperature of from−10 to +150° C., in particular at from 0 to 100° C., under atmosphericor superatmospheric pressure. The diketopyrrolopyrrole sulfochloride isjudiciously precipitated in water and isolated.

The reaction of the sulfochloride with the amine takes place preferablyat a temperature of from 0 to 100° C., in particular at from 0 to 70° C.The molar amounts of amine:sulfochloride are judiciously (from 0.5 to10):1, in particular (1-4):1.

The present invention further provides a pigment preparation comprising

-   a) at least one organic base pigment, and-   b) at least one pigment dispersant of the formula (I).

By base pigments are meant organic pigments or mixtures of organicpigments which may also be present in the form of customary pigmentpreparations. Examples of suitable base pigments for producing thepigment preparations of the invention are perylene, perinone,quinacridone, quinacridonequinone, anthraquinone, anthanthrone,benzimidazolone, disazo condensation, azo, indanthrone, phthalocyanine,triarylcarbonium, dioxazine, aminoanthraquinone, diketopyrrolopyrrole,thioindigo, isoindoline, isoindolinone, pyranthrone, isoviolanthrone andcarbon black pigments or mixtures thereof.

Examples of preferred base pigments for the purposes of the presentinvention are C.I. Pigment Red 123 (C.I. No. 71145), C.I. Pigment Red149 (C.I. No. 71137), C.I. Pigment Red 178 (C.I. No. 71 155), C.I.Pigment Red 179 (C.I. No. 71 130), C.I. Pigment Red 190 (C.I. 71 140),C.I. Pigment Red 224 (C.I. No. 71 127), C.I. Pigment Violet 29 (C.I. No.71 129), C.I. Pigment Orange 43 (C.I. No. 71 105), C.I. Pigment Red 194(C.I. No. 71 100), C.I. Pigment Violet 19 (C.I. No. 73 900), C.I.Pigment Red 122 (C.I. No. 73 915), C.I. Pigment Red 192, C.I. PigmentRed 202 (C.I. No. 73 907), C.I. Pigment Red 207, C.I. Pigment Red 209(C.I. No. 73 905), C.I. Pigment Red 206 (C.I. No. 73 900/73 920), C.I.Pigment Orange 48 (C.I. No. 73 900/73 920), C.I. Pigment Orange 49 (C.I.No. 73 900/73 920), C.I. Pigment Orange 42, C.I. Pigment Yellow 147,C.I. Pigment Red 168 (C.I. No. 59 300), C.I. Pigment Yellow 120 (C.I.No. 11 783), C.I. Pigment Yellow 151 (C.I. No. 13 980), C.I. PigmentBrown 25 (C.I. No. 12 510), C.I. Pigment Violet 32 (C.I. No. 12 517),C.I. Pigment Orange 64; C.I. Pigment Brown 23 (C.I. No. 20 060), C.I.Pigment Red 166 (C.I. No. 20 730), C.I. Pigment Red 170 (C.I. No. 12475), C.I. Pigment Orange 38 (C.I. No. 12 367), C.I. Pigment Red 188(C.I. No. 12 467), C.I. Pigment Red 187 (C.I. No. 12 486), C.I. PigmentOrange 34 (C.I. No. 21 115), C.I. Pigment Orange 13 (C.I. No. 21 110),C.I. Pigment Red 9 (C.I. No. 12 460), C.I. Pigment Red 2 (C.I. No. 12310), C.I. Pigment Red 112 (C.I. No. 12 340), C.I. Pigment Red 7 (C.I.No. 12 420), C.I. Pigment Red 210 (C.I. No. 12 477), C.I. Pigment Red 12(C.I. No. 12 385), C.I. Pigment Blue 60 (C.I. No. 69 800), C.I. PigmentGreen 7 (C.I. No. 74 260), C.I. Pigment Green 36 (C.I. No. 74 265); C.I.Pigment Blue 15:1, 15:2, 15:3, 15:4, 15:6 and 15 (C.I. No. 74 160); C.I.Pigment Blue 56 (C.I. No. 42 800), C.I. Pigment Blue 61 (C.I. No. 42765:1), C.I. Pigment Violet 23 (C.I. No. 51 319), C.I. Pigment Violet 37(C.I. No. 51 345), C.I. Pigment Red 177 (C.I. No. 65 300), C.I. PigmentRed 254 (C.I. No. 56 110), C.I. Pigment Red 255 (C.I. No. 56 1050), C.I.Pigment Red 264, C.I. Pigment Red 270, C.I. Pigment Red 272 (C.I. No. 561150), C.I. Pigment Red 71, C.I. Pigment Orange 73, C.I. Pigment Red 88(C.I. No. 73 312).

In addition to the base pigment a) and the pigment dispersant b), thepigment preparations of the invention may further comprise customaryadditives, such as fillers, standardizers, surfactants, resins,defoamers, antidust agents, extenders, shading colorants, preservatives,drying retarders, and rheology control additives, for example.

Preferred pigment preparations for the purposes of the present inventionconsist essentially of

-   a) from 50 to 99.5% by weight, preferably from 60 to 98,8% by    weight, of at least one base pigment a),-   b) from 0.5 to 20% by weight, preferably from 1 to 15% by weight, of    at least one, preferably 1 or 2, pigment dispersant(s) b) of the    formula (I),-   c) from 0 to 20% by weight, preferably from 0.1 to 15% by weight, of    surfactants, and-   d) from 0 to 20% by weight, preferably from 0.1 to 10% by weight, of    further customary additives,    the fractions of the respective components being based on the    overall weight of the preparation (100% by weight).

Suitable surface-active agents c) include anionic or anion-active,cationic or cation-active, or nonionic substances or mixtures thereof.Examples of suitable anionic substances are fatty acid taurides, fattyacid N-methyltaurides, fatty acid isethionates, alkylphenylsulfonates,alkylnaphthalenesulfonates, alkylphenol polyglycol ether sulfates, fattyalcohol polyglycol ether sulfates; fatty acids, e.g., palmitic, stearicand oleic acid; fatty acid amide polyglycol ether sulfates;alkylsulfosuccinamates; alkenylsuccinic monoesters, fatty alcoholpolyglycol ether sulfosuccinates, alkanesulfonates, fatty acidglutamates, alkylsulfosuccinates, fatty acid sarcosides; soaps, e.g.,alkali metal salts of fatty acids, naphthenic acids and resin acids,e.g., abietic acid, alkali-soluble resins, e.g., rosin-modified maleateresins and condensation products based on cyanuric chloride, taurene,N,N-dialkylaminoalkylamine, such as N,N-diethylaminopropylamine, forexample, and p-phenylenediamine; preference is given to resin soaps,i.e., alkali metal salts of resin acids.

Examples of suitable cationic substances are quaternary ammonium salts,fatty amine oxalkylates, oxalkylated polyamines, fatty amine polyglycolethers, fatty amines, diamines and polyamines derived from fatty aminesor fatty alcohols, and the oxalkylates of these amines; imidazolinesderived from fatty acids, and salts of these cationic substances.

Examples of suitable nonionic substances are amine oxides, fatty alcoholpolyglycol ethers, fatty acid polyglycol esters, betaines, such as fattyacid amide N-propyl betaines, phosphoric esters of fatty alcohols orfatty alcohol polyglycol ethers, fatty acid amide ethoxylates, fattyalcohol-alkylene oxide adducts, and alkylphenol polyglycol ethers.

The pigment preparations of the invention generally comprise solidsystems of free-flowing pulverulent consistency, or granules.

The dispersing effect which can be achieved in accordance with theinvention is assumed to derive from a modification of the surfacestructure of the base pigments by the pigment dispersant as per b). Thusin a range of cases the efficacy of the pigment dispersant as per b) andthe quality of the pigment preparations produced therewith are dependenton the point in time at which the pigment dispersant as per b) is addedin the production process of the base pigment. Where more than onepigment dispersant as per b) is used, the dispersants may be addedsimultaneously or at different points in time or may be mixed prior totheir addition.

The efficacy of the pigment dispersant as per b) may also depend on itsparticle size and particle morphology and on the extent of the availablepigment surface. It may be advantageous to add the pigment dispersant asper b) to the base pigment only in the prospective application medium.The optimum concentration of the pigment dispersant as per b) in eachcase must be determined by means of preliminary rangefinding tests,since the enhancement of the properties of the base pigments is notalways in linear proportion to the amount of pigment dispersant.

The pigment preparations of the invention may comprise mixtures of oneor more, preferably 1 or 2, base pigments with one or more, preferably 1or 2, of the pigment dispersants as per b).

The invention also provides a process for producing a pigmentpreparation of the invention, which comprises mixing the pigmentdispersant(s) as per (b) and the base pigment(s) with one another orcausing them to act on one another at any desired point in time duringtheir production process.

The production process of an organic pigment embraces its synthesis,possibly fine division, by grinding or reprecipitation, for example,possibly finishing, and its isolation as a presscake or in the form ofdry granules or powder. For example, the pigment dispersant as per b)may be added prior to or during the pigment synthesis, immediately priorto or during the fine division process or a subsequent finishing. Thetemperatures prevailing may be, for example, from 0 to 200° C. Thepigment dispersant as per b) can of course also be added in portions atdifferent times.

The addition of the pigment dispersant as per b) as part of a finedivision process takes place, for example, prior to or during the drygrinding of a crude pigment with or without additional millingauxiliaries on a roll mill or vibratory mill, or prior to or during thewet grinding of a crude pigment in an aqueous, aqueous-organic ororganic grinding medium on, for example, a bead mill.

It has also proven suitable to add the pigment dispersant as per b)prior to or after finishing the base pigment in an aqueous,aqueous-alkaline, aqueous-organic or organic medium. The pigmentdispersant as per b) may also be added to the water-moist pigmentpresscake, and incorporated, before drying, in which case the pigmentdispersant as per b) may itself be present as a presscake. A furtherpossibility is to make dry mixes of powders or granules of the pigmentdispersant as per b) with the powder or granules of one or more basepigments, or to effect mixing by grinding or pulverizing components a)and b).

The pigment preparations of the invention are notable for theiroutstanding coloristic and rheological properties, especially foroutstanding rheology, high flocculation stability, high transparency,ease of dispersibility, excellent gloss behavior, high color strength,excellent fastness to overcoating and to solvents, and very good weatherfastness. They are suitable for use both in solventborne and aqueoussystems.

The pigment preparations produced in accordance with the invention maybe used to pigment high molecular mass organic materials of natural orsynthetic origin, examples being plastics, resins, varnishes, paints, orelectrophotographic toners and developers, and also writing, drawing andprinting inks.

Examples of high molecular mass organic materials which may be pigmentedwith the abovementioned pigment preparations are cellulose ethers andcellulose esters, such as ethylcellulose, nitrocellulose, celluloseacetate or cellulose butyrate, natural resins or synthetic resins, suchas addition-polymerization resins or condensation resins, e.g., aminoresins, especially urea-formaldehyde and melamine-formaldehyde resins,alkyd resins, acrylic resins, phenolic resins, polycarbonates,polyolefins, such as polystyrene, polyvinyl chloride, polyethylene,polypropylene, polyacrylonitrile, polyacrylates, polyamides,polyurethanes or polyesters, rubber, casein, silicone and siliconeresins, individually or in mixtures.

It is unimportant here whether the abovementioned high molecular massorganic compounds are present in the form of plastic masses, melts,spinning solutions, varnishes, paints or printing inks. Depending on theintended use it is found advantageous to utilize the pigmentpreparations, obtained in accordance with the invention, as a blend orin the form of prepared formulations or dispersions. Based on the highmolecular mass organic material for pigmentation, the pigmentpreparations of the invention are used in an amount of from 0.05 to 30%by weight, preferably from 0.1 to 15% by weight.

The pigment preparations of the invention are also suitable for use ascolorants in electrophotographic toners and developers, such as one- ortwo-component powder toners (also called one- or two-componentdevelopers), magnetic toners, liquid toners, polymerization toners, andspecialty toners, for example (L. B. Schein, “Electrophotography andDevelopment Physics”; Springer Series in Electrophysics 14, SpringerVerlag, 2nd edition, 1992).

Typical toner binders are addition polymerization, polyaddition andpolycondensation resins, such as styrene, styrene-acrylate,styrene-butadiene, acrylate, polyester, and phenol-epoxy resins,polysulfones, polyurethanes, individually or in combination, and alsopolyethylene and polypropylene, which may include further constituents,such as charge control agents, waxes or flow assistants, or may bemodified subsequently with these additives.

Furthermore, the pigment preparations of the invention are suitable foruse as colorants in powders and powder coating materials, especially intriboelectrically or electrokinetically sprayable powder coatingmaterials, which are used to coat the surfaces of articles made, forexample, of metal, wood, plastic, glass, ceramic, concrete, textilematerial, paper or rubber (J. F. Hughes, “Electrostatics Powder Coating”Research Studies, John Wiley & Sons, 1984).

Typical powder coating resins used are epoxy resins, carboxyl- andhydroxyl-containing polyester resins, polyurethane resins and acrylicresins, together with customary hardeners. Resin combinations are alsoused. For example, epoxy resins are frequently used in combination withcarboxyl- and hydroxyl-containing polyester resins. Typical hardenercomponents (depending on the resin system) are, for example, acidanhydrides, imidazoles and also dicyandiamide and derivatives thereof,blocked isocyanates, bisacylurethanes, phenolic resins and melamineresins, triglycidyl isocyanurates, oxazolines, and dicarboxylic acids.

In addition, the pigment preparations of the invention are suitable foruse as colorants in inkjet inks on either an aqueous or nonaqueous basisand in those inks which operate in accordance with the hot-melt process.

Furthermore, the pigment preparations of the invention are also suitableas colorants for color filters and for both additive and subtractivecolor generation.

It is also possible for the pigment dispersant as per b) to be added tothe base pigment, or vice versa, only in the application medium. Theinvention therefore further provides a prepared pigment formulationconsisting essentially of one or more organic base pigments a), one ormore pigment dispersants as per b), said high molecular mass organicmaterial, especially varnish, and, if desired, surfactant and/or othercustomary additives. The overall amount of base pigment plus pigmentdispersant as per b) is, for example, from 0.05 to 30% by weight,preferably from 0.1 to 15% by weight, based on the overall weight of theprepared pigment formulation.

In order to evaluate the properties in the coatings sector of thepigment preparations, a selection was made, from among the large numberof known varnishes, of an alkyd-melamine resin varnish (AM) containingaromatic components and based on a medium-oil alkyd resin and on abutanol-etherified melamine resin, of a polyester varnish (PE) based oncellulose acetobutyrate and on a melamine resin, of a high-solidsacrylic resin baking varnish based on a nonaqueous dispersion (HS), andof a polyurethane-based aqueous varnish (PUR).

The color strength and shade were determined in accordance with DIN55986. The rheology of the millbase after dispersion (millbase rheology)was evaluated visually on the basis of the following five-point scale:

5 highly fluid 4 liquid 3 viscous 2 slightly set 1 set

Following dilution of the millbase to the final pigment concentration,the viscosity was assessed using the Rossmann viscospatula type 301 fromErichsen.

Gloss measurements were carried out on cast films at an angle of 20° inaccordance with DIN 67530 (ASTMD 523) using the “multigloss” gloss meterfrom Byk-Mallinckrodt. The solvent fastness was determined in accordancewith DIN 55976. The fastness to overcoating was determined in accordancewith DIN 53221.

EXAMPLES

In the examples below, parts and percentages are in each case by weight.“min” are minutes.

The formulae given in the following Examples 1 to 10 and 24 to 26 arebased on formula (I). In each case, the number n is about (2−s), asExample 1a gives a disulfochloride, and E+ means H+.

Example 1a

A four-necked flask is charged with 250 parts of chlorosulfonic acid,and 25 parts of 1,4-diketo-3,6-di(4-biphenyl)pyrrolo[3,4-c]pyrrole areintroduced and dissolved at a rate such that the temperature does notexceed 25° C. Then 19.64 parts of thionyl chloride are added dropwiseover the course of 15 min and the mixture is stirred for 15 min. Overthe course of 15 min, the solution is added dropwise to 1000 parts ofice-water, prepared from 333 parts of ice and 667 parts of water. Theprecipitated disulfochloride is filtered and washed with 750 parts ofcold water. A four-necked flask is charged with 70 parts of ice, 70parts of water and 15.3 parts of 3-dimethylamino-1-propylamine and thedisulfochloride presscake is introduced at from 0 to 5° C. The mixtureis then stirred at 0 to 5° C. for 1 h, heated to 25° C. in 30 min,stirred at 25° C. for 30 min, heated to 50° C. in 30 min, stirred at 50°C. for 30 min, heated to 70° C. in 30 min and stirred at 70° C. for 30min. The product is filtered, washed with water and dried in a forcedair oven at 80° C. This gives 39.9 parts of pigment dispersant. From theintensities of the ¹H-NMR signals, the degree of substitution s iscalculated to be about 1.6.

¹H-NMR (D₂SO₄): δ 7.8; 7.6; 5.9; 3.1; 2.7; 2.5; 1.8 ppm.

Example 1b

30 parts of a standard commercial pigment (C.I. Pigment Red 264) aremixed mechanically with 3 parts of pigment dispersant of the formula Xprepared in accordance with Example 1a.

A pigment preparation is obtained which gives transparent and stronglycolored coatings in the HS varnish. The gloss measurement gives a valueof 65. The metallic coating is strongly colored and bright.

Example 2a

The procedure of Example 1 a is repeated except that the amine usedcomprises 21.63 parts of N-(3-aminopropyl)morpholine. This gives 42.1parts of pigment dispersant.

¹H-NMR (D₂SO₄): δ 7.8; 7.6; 3.9; 3.6; 3.1; 2.8; 1.8 ppm.

From the intensities of the signals, the degree of substitution s iscalculated to be about 1.7.

Example 2b

30 parts of a standard commercial pigment (C.I. Pigment Red 264) aremixed mechanically with 3 parts of pigment dispersant of the formula XIprepared in accordance with Example 2a.

A pigment preparation is obtained which gives transparent and stronglycolored coatings in the HS varnish. The viscosity is 2.6 s. The glossmeasurement gives a value of 75. The metallic coating is stronglycolored and bright.

Example 3a

The procedure of Example 1a is repeated except that the amine usedcomprises 19.38 parts of N-(2-aminoethyl)piperazine. This gives 39.3parts of pigment dispersant.

¹H-NMR (D₂SO₄): δ 7.8; 7.6; 3.6; 3.1 ppm.

From the intensities of the signals, the degree of substitution s iscalculated to be about 1.0.

Example 3b

30 parts of a standard commercial pigment (C.I. Pigment Red 264) aremixed mechanically with 3 parts of pigment dispersant of the formula XIIprepared in accordance with Example 3a. A pigment preparation isobtained which gives transparent and strongly colored coatings in the HSvarnish.

Example 4a

The procedure of Example 1 a is repeated except that the amine usedcomprises 13.22 parts of 3-(methylamino)propylamine. This gives 36.1parts of pigment dispersant.

¹H-NMR (D₂SO₄): δ 7.8; 7.6; 3.2; 2.8; 2.6; 2.4; 1.9; 1.8 ppm.

From the intensities of the signals, the degree of substitution s iscalculated to be about 1.2.

Example 4b

30 parts of a standard commercial pigment (C.I. Pigment Red 264) aremixed mechanically with 3 parts of pigment dispersant of the formulaXIII prepared in accordance with Example 4a. A pigment preparation isobtained which gives transparent and strongly colored coatings in the HSvarnish.

Example 5a

The procedure of Example 1 a is repeated except that the amine usedcomprises 15.62 parts of N-(2-aminoethyl)ethanolamine. This gives 37.5parts of pigment dispersant.

¹H-NMR (D₂SO₄): δ 7.8; 7.6; 4.2; 4.1; 3.2; 3.1 ppm.

From the intensities of the signals, the degree of substitution s iscalculated to be about 1.2.

Example 5b

30 parts of a standard commercial pigment (C.I. Pigment Red 264) aremixed mechanically with 3 parts of pigment dispersant of the formula XIVprepared in accordance with Example 5a. A pigment preparation isobtained which gives transparent and strongly colored coatings in the HSvarnish.

Example 6a

The procedure of Example 1 a is repeated except that the amine usedcomprises 28.5 parts of 3-(dibutylamino)-1-propylamine, 98% pure. Thisgives 47.4 parts of pigment dispersant.

¹H-NMR (D₂SO₄): δ 7.8; 7.6; 3.1; 2.7; 2.6; 1.7; 1.2; 0.9; 0.5 ppm.

From the intensities of the signals, the degree of substitution s iscalculated to be about 1.9.

Example 6b

30 parts of a standard commercial pigment (C.I. Pigment Red 264) aremixed mechanically with 3 parts of pigment dispersant of the formula XVprepared in accordance with Example 6a.

A pigment preparation is obtained which gives transparent and stronglycolored coatings in the HS varnish. The rheology is evaluated as from 4to 5 and the viscosity is 1.1 s. The gloss measurement gives a value of81. The metallic coating is strongly colored and bright.

Without the addition of the pigment dispersant, the HS coatings areweaker in color and substantially more hiding. The rheology is evaluatedas 3 and the viscosity is 16.5 s. The gloss measurement gives a value of52. The metallic coating is markedly weaker in color and less bright.

The coating in the PE varnish is transparent and strongly colored. Thegloss measurement gives a value of 82. The metallic coating is stronglycolored and bright. Without the addition of the pigment dispersant, thePE coatings are weaker in color, markedly more hiding, and so matt thatit is impossible to measure a gloss. The metallic coating issignificantly weaker in color and less bright.

Example 7a

The procedure of Example 1 a is repeated except that the amine usedcomprises 15.77 parts of 2-(2-aminoethoxy)ethanol. This gives 40.5 partsof pigment dispersant.

¹H-NMR (D₂SO₄): δ 7.8; 7.6; 4.1; 3.5; 3.3; 2.9 ppm.

From the intensities of the signals, the degree of substitution s iscalculated to be about 1.6.

Example 7b

30 parts of a standard commercial pigment (C.I. Pigment Red 264) aremixed mechanically with 3 parts of pigment dispersant of the formula XVIprepared in accordance with Example 7a. A pigment preparation isobtained which gives transparent and strongly colored coatings in the HSvarnish.

Example 8a

The procedure of Example 1a is repeated except that the amine usedcomprises 13.78 parts of 2-amino-1-butanol. This gives 36.6 parts ofpigment dispersant.

¹H-NMR (D₂SO₄): δ 7.8; 7.6; 4.3; 4.1; 3.7; 1.5; 0.6 ppm.

From the intensities of the signals, the degree of substitution s iscalculated to be about 1.4.

Example 8b

30 parts of a standard commercial pigment (C.I. Pigment Red 264) aremixed mechanically with 3 parts of pigment dispersant of the formulaXVII prepared in accordance with Example 8a. A pigment preparation isobtained which gives transparent and strongly colored coatings in the HSvarnish.

Example 9a

The procedure of Example 1 a is repeated except that the amine usedcomprises 21.33 parts of 1-(3-aminopropyl)-2-pyrrolidinone. This gives42.2 parts of pigment dispersant.

¹H-NMR (D₂SO₄): δ 7.8; 7.6; 3.4; 3.2; 2.9; 2.7; 1.8; 1.7 ppm.

From the intensities of the signals, the degree of substitution s iscalculated to be about 1.6.

Example 9b

30 parts of a standard commercial pigment (C.I. Pigment Red 264) aremixed mechanically with 3 parts of pigment dispersant of the formulaXVIII prepared in accordance with Example 9a. A pigment preparation isobtained which gives transparent and strongly colored coatings in the HSvarnish.

Example 10a

The procedure of Example 1 a is repeated except that the amine usedcomprises 19.54 parts of diethylaminopropylamine. This gives 41.3 partsof pigment dispersant.

¹H-NMR (D₂SO₄): δ 7.8; 7.6; 3.1; 2.7; 1.7; 0.8 ppm.

From the intensities of the signals, the degree of substitution s iscalculated to be about 1.7.

The solvent fastness of the dispersant is very good.

Example 10b

30 parts of a standard commercial pigment (C.I. Pigment Red 264) aremixed mechanically with 3 parts of pigment dispersant of the formula XIXprepared in accordance with Example 10a.

A pigment preparation is obtained whose solvent fastness is very goodand which gives transparent and strongly colored coatings in the HSvarnish. The rheology is evaluated as 4-5 and the viscosity is 1.8 s.The gloss measurement gives a value of 71. The metallic coating isstrongly colored and bright.

Without the addition of the pigment dispersant, the HS coatings areweaker in color and substantially more hiding. The rheology is evaluatedas 3 and the viscosity is so high that it cannot be measured using theviscospatula. The gloss as well is impossible to measure, owing to thesevere flocculation. The metallic coating is notably weaker in color andless bright.

The coating in the PE varnish is transparent and strongly colored. Thegloss measurement gives a value of 33. The metallic coating is stronglycolored and bright. Without the addition of the pigment dispersant, thePE coatings are weaker in color, markedly more hiding, and so matt thatit is impossible to measure a gloss. The metallic coating issignificantly weaker in color and less bright.

The coating in the AM varnish is transparent and strongly colored. Thegloss measurement gives a value of 89. The viscosity is 5.4 s.

Without the addition of the pigment dispersant, the AM coatings areweaker in color, significantly more hiding and so matt that the glosscannot be measured. The viscosity is so high that it cannot be measuredusing the viscospatula.

Example 10c

28.5 parts of a standard commercial pigment (C.I. Pigment Red 264) aremixed mechanically with 1.5 parts of pigment dispersant of the formulaXIX prepared in accordance with Example 10a. The solvent fastness of thepigment preparation is very good.

Example 11a

(Comparative Example A, Pigment Dispersant of the Formula XX FromJP-H3-26767, Example 1)

The pigment dispersant of the formula XX is prepared as described inJP-H3-26767, Example 1.

¹H-NMR (D₂SO₄): δ 8.0; 7.9; 7.8; 7.7; 3.1; 2.7; 1.7; 0.8 ppm.

From the intensities of the signals, the degree of substitution, s, iscalculated to be about 1.2.

The solvent fastness of the pigment preparation is inadequate. Incomparison to the solvent fastness of the pigment preparation of theformula XIX prepared in accordance with Example 10a it is significantlypoorer and thus distinctly inferior.

Example 11b

(Comparative Example B: Pigment Preparation Containing PigmentDispersant From JP-H3-26767, Example 1)

28.5 parts of a standard commercial pigment (C.I. Pigment Red 264) aremixed mechanically with 1.5 parts of pigment dispersant of the formulaXX prepared in accordance with Example 11a.

The solvent fastness of the pigment preparation is inadequate. Incomparison to the solvent fastness of the pigment preparation preparedin accordance with Example 10c it is significantly poorer and thusdistinctly inferior.

Example 12a PE Varnish

A coating is prepared in the PE varnish using the pigment preparationprepared as in Example 10c. The fastness to overcdating is excellent,with no evidence of bleeding. A coating is prepared in the PE varnishusing the pigment preparation prepared as in Example 11b. The fastnessto overcoating is deficient, with severe bleeding being visible.

Example 12b PUR Varnish

A coating is prepared in the PUR varnish using the pigment preparationprepared as in Example 10c. The fastness to overcoating is excellent,with no evidence of bleeding.

A coating is prepared in the PUR varnish using the pigment preparationprepared as in Example 11b. The fastness to overcoating is unacceptable,with very severe bleeding being visible.

Example 13a

(Comparative Example C: Pigment Dispersant of the Formula (XX) Accordingto Example 10a)

The pigment dispersant of the formula XX is prepared as per Example 10awith the sole difference that, instead of 25 parts of1,4-diketo-3,6-di-(4-biphenyl)pyrrolo[3,4-c]pyrrole, 16.4 parts of1,4-diketo-3,6-diphenylpyrrolo[3,4-c]pyrrole are used. This gives 17.2parts of pigment dispersant.

¹H-NMR (D₂SO₄): δ 8.0; 7.9; 7.8; 7.7; 3.1; 2.7; 1.7; 0.8 ppm.

From the intensities of the signals, the degree of substitution s iscalculated to be about 0.12.

The solvent fastness of the pigment preparation is inadequate. Incomparison to the solvent fastness of the pigment preparation of theformula XIX prepared in accordance with Example 10a it is significantlypoorer and thus distinctly inferior.

Example 13b

(Comparative Example D: Pigment Preparation Containing PigmentDispersant of the Formula (XX) From Example 13a)

30 parts of a standard commercial pigment (C.I. Pigment Red 264) aremixed mechanically with 3 parts of pigment dispersant of the formula(XX) prepared in accordance with Example 13a.

The solvent fastness of the pigment preparation is inadequate. Incomparison to the solvent fastness of the pigment preparation preparedin accordance with Example 10c it is significantly poorer and thusdistinctly inferior.

Example 14a PE Varnish

A coating is prepared in the PE varnish using the pigment preparationprepared as in Example 10b. The coating is transparent and stronglycolored, the gloss measurement gives a value of 33. The metallic coatingis strongly colored and bright. The fastness to overcoating isexcellent, with no evidence of bleeding.

A coating is prepared in the PE varnish using the pigment preparationprepared as in Example 13b. Compared with the above coating, it ismarkedly more hiding, substantially weaker in color, the gloss isimpossible to measure owing to the severe flocculation, and the metalliccoating is substantially weaker in color and paler. The fastness toovercoating is deficient, with severe bleeding being visible.

Example 14b PUR Varnish

A coating is prepared in the PUR varnish using the pigment preparationprepared as in Example 10b. The fastness to overcoating is excellent,with no evidence of bleeding.

A coating is prepared in the PUR varnish using the pigment preparationprepared as in Example 13b. The fastness to overcoating is unacceptable,with very severe bleeding being visible.

Example 14c HS Varnish

A coating is prepared in the HS varnish using the pigment preparationprepared as in Example 10b. This coating is transparent and stronglycolored. The rheology is assessed as from 4 to 5 and the viscosity is1.8 s. The gloss measurement gives a value of 71. The metallic coatingis strongly colored and bright. The fastness to overcoating isexcellent.

A coating is prepared in the HS varnish using the pigment preparationprepared as in Example 13b. Compared with the above coating, it isnotably weaker in color. The rheology is evaluated as only 3 and theviscosity has increased to 3.0 s. The gloss measurement gives a value ofonly 43. The metallic coating is substantially weaker in color andpaler. The test of fastness to overcoating shows marked bleeding.

Example 15

20 parts of a standard commercial pigment (C.I. Pigment Red 177) aremixed mechanically with 1 part of pigment dispersant of the formula XVprepared in accordance with Example 6a.

A pigment preparation is obtained which gives coatings in the HS varnishwhich, compared with the coatings of the untreated standard commercialpigment (C.I. Pigment Red 177), are more transparent, more glossy anddistinctly stronger in color; the masstone coatings of the untreatedstandard commercial pigment (C.I. Pigment Red 177) show a haze. Themetallic coatings of the prepared pigment formulation are significantlycleaner and brighter than the metallic coatings of the untreatedstandard commercial pigment (C.I. Pigment Red 177).

In the PE varnish, the coatings of the pigment preparation are moretransparent, substantially stronger in color and more glossy, and themetallic coatings are substantially stronger in color and brighter thanthe corresponding coatings of the untreated standard commercial pigment(C.I. Pigment Red 177).

Example 16

20 parts of a standard commercial pigment (C.I. Pigment Brown 25) aremixed mechanically with 1 part of pigment dispersant of the formula XVprepared in accordance with Example 6a.

A pigment preparation is obtained which in the HS varnish gives coatingswhich, compared with the coatings of the untreated standard commercialpigment (C.I. Pigment Brown 25), are stronger in color. The metalliccoatings of the prepared pigment formulation are stronger in color andbrighter.

Example 17

20 parts of a standard commercial pigment (C.I. Pigment Violet 23) aremixed mechanically with 1 part of pigment dispersant of the formula XVprepared in accordance with Example 6a.

A pigment preparation is obtained which in the HS varnish gives coatingswhich, compared with the coatings of the untreated standard commercialpigment (C.I. Pigment Violet 23), are more transparent, stronger incolor and substantially redder. The metallic coatings of the preparedpigment formulation are stronger in color, brighter and substantiallyredder than the metallic coatings of the untreated standard commercialpigment (C.I. Pigment Violet 23).

In the PE varnish, the coatings of the pigment preparation are moretransparent, stronger in color and markedly redder, and the metalliccoatings are stronger in color and redder than the correspondingcoatings of the untreated standard commercial pigment (C.I. PigmentViolet 23).

Example 18

20 parts of a standard commercial pigment (C.I. Pigment Violet 19,β-phase) are mixed mechanically with 1 part of pigment dispersant of theformula XV prepared in accordance with Example 6a.

A pigment preparation is obtained which in the PE varnish gives coatingswhich, compared with the coatings of the untreated standard commercialpigment (C.I. Pigment Violet 19, β-phase), are more transparent,stronger in color and cleaner. The metallic coatings of the preparedpigment formulation are markedly stronger in color and brighter than themetallic coatings of the untreated standard commercial pigment (C.I.Pigment Violet 19, β-phase).

Example 19

20 parts of a standard commercial pigment (C.I. Pigment Blue 15:1) aremixed mechanically with 1 part of pigment dispersant of the formula XVprepared in accordance with Example 6a.

A pigment preparation is obtained which in the HS varnish gives coatingswhich, compared with the coatings of the untreated standard commercialpigment (C.I. Pigment Blue 15:1), are more transparent, more glossy andstronger in color. The metallic coatings of the prepared pigmentformulation are stronger in color and brighter than the metalliccoatings of the untreated standard commercial pigment (C.I. Pigment Blue15:1).

In the PE varnish, the coatings of the pigment preparation are moretransparent and the metallic coatings are substantially stronger incolor and brighter than the corresponding coatings of the untreatedstandard commercial pigment (C.I. Pigment Blue 15:1).

Example 20

20 parts of a standard commercial pigment (C.I. Pigment Blue 60) aremixed mechanically with 1 part of pigment dispersant of the formula XVprepared in accordance with Example 6a.

A pigment preparation is obtained which in the HS varnish gives stronglycolored and transparent coatings; the metallic coatings are stronglycolored and bright.

Example 21

20 parts of a standard commercial pigment (C.I. Pigment Red 179) aremixed mechanically with 1 part of pigment dispersant of the formula XVprepared in accordance with Example 6a.

A pigment preparation is obtained which in the HS varnish gives coatingswhich, compared with the coatings of the untreated standard commercialpigment (C.I. Pigment Red 179), are more transparent, more stronglycolored and more glossy. The metallic coatings of the prepared pigmentformulation are more strongly colored and brighter.

Example 22

20 parts of a standard commercial pigment (C.I. Pigment Red 202) aremixed mechanically with 1 part of pigment dispersant of the formula XVprepared in accordance with Example 6a.

A pigment preparation is obtained which in the HS varnish givestransparent and strongly colored coatings; the metallic coatings arestrongly colored and bright.

Example 23

298.7 g of tert-amyl alcohol are charged to a vessel and 20.0 g ofsodium are added. The mixture is then heated to boiling and stirreduntil all of the sodium has reacted. After the batch has been cooled to80° C., 57.8 g of p-chlorobenzonitrile are introduced. The mixture isheated to 98-100° C. and 62.7 g of diisopropyl succinate are addeddropwise over the course of 2 hours. The mixture is subsequently stirredat boiling for 3 hours and 45 minutes. After the mixture has cooled to95° C., 3 g of pigment dispersant of the formula XV, prepared inaccordance with Example 6a, are added, the mixture is brought back toboiling and is stirred at boiling for 15 minutes. The reactionsuspension is cooled to 80° C. and poured with stirring into 450 g ofwater heated to 80° C. beforehand. The mixture is heated to boiling andstirred at boiling for 4 hours and 45 minutes. The alcohol is thenremoved by steam distillation. The pigment suspension is filtered andthe solid product is washed salt-free with hot water and dried underreduced pressure at 80° C. This gives 72.2 g of pigment preparation. Inthe HS varnish, the pigment preparation gives transparent and stronglycolored coatings, the rheology is evaluated as 5, and the glossmeasurement gives a value of 67.

Example 24a

A four-necked flask is charged with 250 parts of chlorosulfonic acid,and 25 parts of 1,4-diketo-3,6-di(4-biphenyl)pyrrolo[3,4-c]pyrrole areintroduced and dissolved at a rate such that the temperature does notexceed 25° C. Then 19.64 parts of thionyl chloride are added dropwiseover the course of 15 min and the mixture is stirred for 15 min. Overthe course of 15 min, the solution is added dropwise to 1000 parts ofice-water, prepared from 333 parts of ice and 667 parts of water. Theprecipitated disulfochloride is filtered and washed with 750 parts ofcold water. A four-necked flask is charged with 70 parts of ice, 70parts of water and 23.4 parts of N-cyclohexyl-1,3-propanediamine and thedisulfochloride presscake is introduced at from 0 to 5° C. The mixtureis then stirred at 0 to 5° C. for 1 h, heated to 25° C. in 30 min,stirred at 25° C. for 30 min, heated to 50° C. in 30 min, stirred at 50°C. for 30 min, heated to 70° C. in 30 min and stirred at 70° C. for 30min. The product is filtered and washed with water. The presscake issuspended in 782 parts of water and the pH of the suspension is adjustedto 8.6 using a little aqueous sodium hydroxide solution. Steam is passedthrough the suspension and condensed until about 860 parts of distillatehave been obtained. The product is filtered, washed with water and driedin a forced air oven at 80° C. This gives 43.7 parts of pigmentdispersant.

From the intensities of the signals, the degree of substitution s iscalculated to be about 1.5.

¹H-NMR (D₂SO₄): δ 7.8; 7.6; 5.5; 3.1; 2.7; 1.7; 1.6; 1.4; 1.2; 0.9; 0.7ppm.

Example 24b

20 parts of a standard commercial pigment (C.I. Pigment Red 264) aremixed mechanically with 2 parts of pigment dispersant of the formula XXIprepared in accordance with Example 24a.

A pigment preparation is obtained which gives transparent and stronglycolored coatings in the HS varnish. The viscosity is 2.5 s. The glossmeasurement gives a value of 78. The metallic coating is stronglycolored and bright.

Example 25a

The procedure of Example 24a is repeated except that the amine usedcomprises 22.3 parts of 2-(diisopropylamino)ethylamine. This gives 40.2parts of pigment dispersant.

From the intensities of the signals, the degree of substitution s iscalculated to be about 1.5.

¹H-NMR (D₂SO₄): δ 7.8; 7.7; 7.6; 5.5; 3.3; 3.0; 0.9 ppm.

Example 25b

20 parts of a standard commercial pigment (C.I. Pigment Red 264) aremixed mechanically with 2 parts of pigment dispersant of the formulaXXII prepared in accordance with Example 25a.

A pigment preparation is obtained which gives transparent and stronglycolored coatings in the HS varnish. The viscosity is 1.5 s. The glossmeasurement gives a value of 80. The metallic coating is stronglycolored and bright.

Example 26a

The procedure of Example 24a is repeated except that the amine usedcomprises 24.5 parts of 2-amino-5-diethylaminopentane. The presscake issuspended in 796 parts of water and the pH of the suspension is adjustedto 8.7 using a little aqueous sodium hydroxide solution. Steam is passedthrough the suspension and condensed until about 870 parts of distillatehave been produced. The product is filtered, washed with water and driedat 80° C. in a forced air oven. This gives 41.6 parts of pigmentdispersant.

From the intensities of the signals, the degree of substitution s iscalculated to be about 1.7.

¹H-NMR (D₂SO₄): δ 7.8; 7.6; 5.4; 3.7; 2.7; 2.6; 1.5; 1.3; 1.0; 0.8 ppm.

Example 26b

20 parts of a standard commercial pigment (C.I. Pigment Red 264) aremixed mechanically with 2 parts of pigment dispersant of the formulaXXIII prepared in accordance with Example 26a.

A pigment preparation is obtained which gives transparent and stronglycolored coatings in the HS varnish. The viscosity is 1.5 s. The glossmeasurement gives a value of 78. The metallic coating is stronglycolored and bright.

Example 27a

The procedure of Example 10a is repeated except that instead of 19.54parts only 7.16 parts of diethylaminopropylamine are used.

This gives 36.7 g of pigment dispersant.

¹H-NMR (D₂SO₄): δ 7.8; 7.6; 3.1; 2.7; 1.7; 0.8 ppm.

From the intensities of the signals, a degree of substitution s of about0.8 is calculated; this indicates a degree of substitution n of about0.9.

Example 27b

40 parts of a standard commercial pigment (C.I. Pigment Red 264) aremixed mechanically with 4 parts of pigment dispersant of the formulaXXIV prepared in accordance with Example 27a. The solvent fastness ofthe pigment preparation is very good. The pigment preparation obtainedgives transparent and strongly colored coatings in the PUR varnish.

1. A pigment dispersant of the formula (I):

in which Q is a radical of the diketopyrrolopyrrole compound of theformula (Ia):

s is a number from 0.1 to 4.0, n is 2-s, E⁺ is H⁺ or the equivalentM^(m+)/m of a metal cation M^(m+) from main groups 1 to 5 or transitiongroups 1 or 2 or 4 to 8 of the periodic system of the chemical elements,m being 1, 2 or 3, an ammonium ion N⁺R⁹R¹⁰R¹¹R¹², where the substituentsR⁹, R¹⁰, R¹¹ and R¹² independently of one another are each a hydrogenatom, C₁-C₃₀-alkyl, C₂-C₃₀-alkenyl, C₅-C₃₀-cycloalkyl, phenyl,(C₁-C₆)-alkyl-phenyl, (C₁-C₄)-alkylene-phenyl, or a (poly)alkyeneoxygroup of the formula —[CH(R⁸⁰)—CH(R⁸⁰)—O]_(k)—H, in which k is a numberfrom 1 to 30 and the two radicals R⁸⁰ independently of one another arehydrogen, C₁-C₄-alkyl or, if k is >1, a combination thereof; and inwhich alkyl, alkenyl, cycloalkyl, phenyl or alkylphenyl R⁹, R¹⁰, R¹¹,and/or R¹² may be substituted by amino, hydroxyl and/or carboxyl; orwhere the substituents R⁹ and R¹⁰, together with the quaternary nitrogenatom, are able to form a five- to seven-membered saturated ring systemcontaining, if desired, further heteroatoms from the group consisting ofO, S and N, or where the substituents R⁹, R¹⁰ and R¹¹, together with thequaternary nitrogen atom, are able to form a five- to seven-memberedaromatic ring system, containing, if desired, further heteroatoms fromthe group consisting of O, S and N, and to which additional rings may befused if desired, and in which the two radicals Z are identical ordifferent and Z has the definition Z¹ or Z⁴, where Z¹ is a radical ofthe formula (Ib):—[X—Y]_(q)R³  (Ib) in which X is a C₂-C₈-alkylene radical, aC₅-C₇-cycloalkylene radical, or a combination of these radicals, itbeing possible for these radicals to be substituted by from 1 to 4C₁-C₄-alkyl radicals, hydroxyl radicals, (C₁-C₄)-hydroxyalkyl radicalsand/or by 1 or 2 further C₅-C₇-cycloalkyl radicals, or in which X, if qis >1, may also be a combination of said definitions; Y is a —O—,

or —NR²— group, or in which Y, if q is >1, may also be a combination ofsaid definitions; q is a number from 1 to 10; R² and R³ independently ofone another are a hydrogen atom, a substituted or unsubstituted, orpartly fluorinated or perfluorinated, branched or unbranched(C₁-C₂₀)-alkyl group, a substituted or unsubstituted C₅-C₇-cycloalkylgroup or a substituted or unsubstituted, or partly fluorinated orperfluorinated (C₂-C₂₀)-alkenyl group, it being possible for thesubstituents to be hydroxyl, phenyl, cyano, chloro, bromo, amino,C₂-C₄-acyl or C₁-C₄-alkoxy, or R² and R³, together with the nitrogenatom, form a saturated, unsaturated or aromatic heteracyclic 5- to7-membered ring containing, if desired, 1 or 2 further nitrogen, oxygenor sulfur atoms or carbonyl groups in the ring, being substituted ifdesired by 1.2 or 3 of the radicals OH, phenyl, CN, Cl, Br, C₁-C₄-alkyl,C₁-C₄-alkoxy, C₂-C₄ acyl and carbamoyl, and carrying, if desired, 1 or 2benzo-fused saturated, unsaturated or aromatic, carbocyclic orheterocyclic rings; and where Z₄ is hydrogen, hydroxyl, amino, phenyl,(C₁-C₄)-alkylene-phenyl, C₆-C₇-cycloalkyl or C₁-C₂₀-alkyl, it beingpossible for the phenyl ring, the (C₁-C₄)-alkylene-phenyl group and thealkyl group to be substituted by one or more substituents from the groupconsisting of Cl, Br, CN, NH₂, OH, C₆H₅, mono-, di- ortri-C₁-C₄-alkoxy-substituted C₆H₆, carbamoyl, C₂-C₄-acyl andC₁-C₄-alkoxy, and it being possible for the phenyl ring and the(C₁-C₄)-alkylene-phenyl group to be substituted by NR²R², or the alkylgroup is perfluorinated or partly fluorinated.
 2. The pigment dispersantas claimed in claim 1, wherein s is a number from 0.2 to 3.0 and n is anumber from 0 to 0.5.
 3. The pigment dispersant as claimed in claim 1,wherein R² and R³, together with the adjacent nitrogen atom, form animidazolyl, piperidinyl, morpholinyl, pipecolinyl, pyrrolyl,pyrrolidinyl, pyrazolyl, pyrrolidinonyl, indolyl or piperazinyl ring. 4.The pigment dispersant as claimed in claim 1, wherein Z¹ has thedefinition —[(CH₂)₃—NH]₂—H, —(CH₂—CH₂—NH)₂H,—(CH₂)₃—NH—(CH₂)₂—NH—(CH₂)₃—NH₂,

—(CH₂)₃—N(CH₃)—(CH₂)₃—NH₂, —(CH₂)₃—O—(CH₂)₂—O —(CH₂)₃—NH₂,—(CH₂)₃—O—(CH₂)₃—O—(CH₂)₃—NH₂, —(CH₂)₂—NH₂, —(CH₂)₃—NH₂,—(CH₂)₃—NH—(CH₂)₂—NH₂, —(CH₂—CH₂—NH)₃—H, —(CH₂—CH₂—NH)₄—H, —(CH₂—CH₂—NH)₅—H, —(CH₂)₃—O—(CH₂)₂—O—(CH₂)₂—O—(CH₂)₃—NH₂,—(CH₂)₃—O—(CH₂)₄—O—(CH₂)₃—NH₂,

—(CH₂)₂—OH, —(CH₂)₃—OH, —CH₂—CH(CH₃)—OH, —CH(CH₂—CH₃)CH₂—OH,—CH(CH₂OH)₂, —(CH₂)₂—O—(CH₂)₂—OH or —(CH₂)₃—O—(CH₂)₂—O—(CH₂)₂—OH;—(CH₂)₂—NH₂, —(CH₂)₃—NH₂, —CH₂—CH(CH₃)—NH₂, —CH₂—C(CH₃)₂—CH₂—NH₂,

—(CH₂)₂—NH—CH₃, —(CH₂)₂—N(CH₃)₂, —(CH₂)₂—NH—CH₂—CH₃,—(CH₂)₂—N(CH₂—CH₃)₂, —(CH₂)₃—NH—CH₃. —(CH₂)₃—N(CH₃)₂, —(CH₂)₃—NH—CH₂—CH₃or —(CH₂)₃—N(CH₂—CH₃)₂,
 5. The pigment dispersant as claimed claim 1,wherein Z⁴ has the definition hydrogen, amino, phenyl, benzyl,NR²R³-substituted phenyl or benzyl, C₁-C₆-alkyl, or a C₂-C₈-alkyl,phenyl or benzyl substituted by 1 or 2 substituents from the groupconsisting of hydroxyl, acetyl, methoxy and ethoxy.
 6. The pigmentdispersant as claimed in claim 1, wherein X is a C₂-C₄-alkylene radicalor cyclohexylene.
 7. A process for preparing a pigment dispersant asclaimed in claim 1 comprising the steps of chlorosulfonating adiketopyrrolopyrrole compound of the formula (Ia):

and reacting the resultant sulfochloride with an amine of the formula(V):


8. A pigment preparation comprising a) at least one organic basepigment, and b) at least one pigment dispersant of the formula (I) asclaimed in claim
 1. 9. The pigment dispersant as claimed in claim 1,wherein s is a number from 0.5 to 2.5 and n is a number from 0 to 0.2.